JPH08188690A - Cementing material for use in chemical fixing technique - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reactive synthetic resin for chemical fixing technique which is almost nonreleasing, exhibits well-balanced good mechanical characteristics, esp. good properties to cross-link with a silicate material, in the cured state, and hence exhibits high resistance to pullout and sufficient hydrolysis resistance and thermal stability.

SOLUTION: The bonding material for chemically fixing an anchor bolt, a sleeve screwed in, or a screw in a perforation contains a synthetic resin curative and a low-releasing reactive synthetic resin which is curable by a free radical method, is being kept in a separated state, and is prepd. from a monomer mixture contg. 10-80 wt.% t-butylstyrene.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bonding material for a chemical fixing technique and a cartridge containing the same.

[0002]

2. Description of the Related Art It has long been known to use a reactive synthetic resin mainly composed of unsaturated polyester resin, vinyl ester resin or epoxy resin as a bonding agent for a chemical fixing technique. This is a two-component agent, one component being a reactive synthetic resin and the other component being a curing agent. Other conventional ingredients are solvents, including fillers, accelerators, stabilizers, reactive solvents (comonomer). These are added to one or the other or both of both components. By mixing the two components, the reaction is initiated while forming free radicals and the synthetic resin cures to give the duromer.

Cartridges having two hollow chambers that contain both components in isolation have been used in the past to secure anchors in bores formed in concrete or rock (eg European patents). Application open 150
555). The cartridge is inserted into the perforation and the fastener is pushed into the perforation by impacting or tapping and rotating, destroying the cartridge and thus both cavities. The reaction is initiated by the mixing of both fixing components, and the cured reactive resin material can transfer the load to the base body without expansive force. Such shear-bonding has proven to be extremely useful, especially for anchoring heavy loads.

Two-chamber cartridges can be used, in particular, for fixing porous or hollow substrates, in particular aerated block blocks, rocks, bricks in concrete. The two-component bonding material is extruded from the cartridge, mixed and pressed into the perforations by means of a suitable device, such as a screw. A fixture having any cross-sectional shape can then be pressed directly into the bonding material, and after the resin has hardened, the fixture can be locked in the perforations. Alternatively, a sleeve with an inner or internal thread is first inserted into the bore, which is fixed to the basic body by hardening the resin and then the screw or tightening bolt is screwed in. In the case of aerated bricks, a plastic or metal lattice cylindrical sleeve is first inserted into the perforation and then the joining material extruded from the two-chamber cartridge is pressed into the sleeve from the lattice of the sleeve, After the synthetic resin has hardened, it provides a firm locking or anchor. The cartridge filled with the foaming adhesive is behind the gypsum board,
Or used for locking in hollow bricks. One component of the bonding material is an inorganic carbonate, such as chalk,
The other component contains an acid, for example polyacrylic acid or phosphoric acid. An inner threaded sleeve is inserted into the bore and the expandable bonding material is press fit into the sleeve. When both components are mixed, carbon dioxide gas is released and the bonding agent is foamed, which fills the inside of the cavity or forms a mushroom-like anchor behind the gypsum board, and by hardening the bonding material, the fixing point in this anchor Is fixed.

Styrene is commonly used as a reactive diluent to provide good synthetic resin viscosity.
Reactive synthetic resins based on styrene have a fast curing rate, but styrene as a comonomer gives off a bad odor, and while manufacturing the bonding material and while using the cartridge You are stunned by the stench. The unsaturated polyester resin-based bonding material containing styrene is further insufficient in stability against hydrolysis.
Furthermore, its thermal stability against fire is also insufficient.

Styrene can be replaced by various other comonomers, especially high-boiling point methacrylates, but the corresponding low-emission, reactive synthetic resins, especially unsaturated polyesters, do not cure completely and are therefore mainly used. The joining material used has extremely low pull-out resistance.

[0007]

SUMMARY OF THE INVENTION The object of the present invention or the object of this technical field is therefore to provide a non-emissive, well-balanced good mechanical property in the cured state,
In particular, a reactive synthetic resin for chemical immobilization technology that exhibits good cross-engagement with silicate materials and therefore high withdrawal force and sufficient hydrolytic and thermal stability. Is to provide.

[0008]

However, it has been found by the present inventors that the above-mentioned problems and objects can be solved or achieved by using t-butylstyrene as a comonomer. Therefore, the present invention also comprises (I) a low-release, reactive synthetic resin curable by the free radical method, which is applied away from the object to be immobilized, and (I
I) for chemically fixing anchor bolts, screwed sleeves and screws in perforations, containing a synthetic resin hardener, the synthetic resin containing 10 to 80% by weight of t-butylstyrene as comonomer. Regarding the bonding material.

The above-mentioned t-butyl styrene is described in some patent documents as a suitable comonomer for unsaturated polyester resins, replacing styrene and substituted styrenes. However, no suitable comonomers for low-release synthetic resins are mentioned anywhere in these known documents.

Suitable reactive synthetic resins are unsaturated polyesters, vinyl ester resins, vinyl ester urethane resins and mixtures thereof.

(1) Unsaturated polyesters A are polybasic, especially dibasic carboxylic acids and their esterifiable derivatives, especially anhydrides, and polyhydric, especially dihydric alcohols. Is a conventional condensate. The alcohols mentioned may additionally contain monobasic carboxylic acid groups or monohydric alcohol groups or hydroxycarboxylic acid groups. However, at least some of these groups must contain ethylenically unsaturated copolymerizable groups. Suitable polyhydric, especially dihydric, unsaturated or saturated alcohols are alkanediols and oxaalkanediols, especially acyclic or cyclic groups or both, such as ethylene glycol, 1,2-propylene glycol. 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, polyethylene glycol 1,2-cyclohexanediol, 2,2-bis (p-hydroxycyclohexyl) -propane, trimethylolpropane, monoallyl ether and 1,4-butenediol. Especially ethylene glycol, propylene glycol, dipropylene glycol, and mixtures thereof are preferred.

Mono-, tri- or even polyhydric alcohols such as ethylhexanol, fatty alcohols, benzyl alcohol, 1,2-di (allyloxy) -propanol-3, glycerol, pentaerythritol, trimethylolpropane are also incidental. Can be used only in small amounts. Polyhydric, especially dihydric alcohols are generally stoichiometric amounts of polybasic, especially dibasic carboxylic acids,
Or it may react with a condensable derivative thereof.

Suitable carboxylic acids or their derivatives are dibasic, olefinically unsaturated, especially α, β olefinically unsaturated carboxylic acids, such as maleic acid, fumaric acid,
Chloromaleic acid, itaconic acid, citraconic acid, methylene glutaric acid, mesaconic acid, or their esters,
Or these anhydrides. Still other modified, dibasic, unsaturated and / or saturated aromatic carboxylic acids such as succinic acid, glutaric acid, α-methylglutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic anhydride, o
-Addition of phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid, endomethylenetetrachlorophthalic acid Can be present as condensation units in the polyester. Also, monobasic, tribasic and polybasic carboxylic acids such as ethylhexanoic acid, fatty acids, methacrylic acid, propionic acid, benzoic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4,5- The same applies to benzenetetracarboxylic acid. Maleic acid, its anhydrides, fumaric acid, o-phthalic anhydride are particularly preferably used.

The molar ratio of unsaturated or saturated dicarboxylic acid is preferably 1: 0 to 1: 2.5.

As the unsaturated polyester, those having a terminal double bond are also suitable.

The unsaturated polyester is 0.5 to 10
0, especially an acid value of 2 to 50, about 800 to 6000,
In particular, it has an average molecular weight of about 1000 to 4000.

Unsaturated polyesters are generally produced by melt condensation of the starting materials or under azeotropic conditions at temperatures of from 150 to 220 ° C. either continuously or batchwise.

Suitable unsaturated polyesters are those modified with cyclopentene or cyclohexene groups.

(2) The unsaturated vinyl ester resin (epoxy acrylate) is an adduct of polyepoxide and unsaturated monocarboxylic acid, especially methacrylic acid. For these resins, for example, US Pat.
No. 3,179,623, and vinyl ester resins containing bisphenol A as a main component are advantageously used. It combines excellent toughness with good resistance to chemicals and heat distortion. On the other hand, as described in, for example, US Pat. No. 3,256,226, a vinyl ester resin obtained from an epoxy novolac resin and (meth) acrylic acid exhibits high heat distortion resistance, but its toughness is low.

The groups shown below are typical of this type of vinyl ester resin.

[0021]

Embedded image However, R in the formula means H or CH ₃ .

Further, other vinyl ester resins are, for example, as shown in European Patent Application No. 534201, an esterification product of (meth) acrylic acid of bisphenol A which is alkoxylated or not alkoxylated. Is.

(3) The unsaturated vinyl ester urethane resin (urethane acrylate) generally has the following groups.

[0024]

Embedded image (C) —O—R ³ —O— (R ³ represents an aliphatic, alicyclic or aromatic group having 2 to 100 carbon atoms) The vinyl ester urethane resin is a polyfunctional isocyanate, and if necessary. It is preferably a reaction product of a polyhydric alcohol, optionally a polyfunctional amine and a hydroxyalkyl (meth) acrylate. However, in this reaction, the weight ratio of the isocyanate (alcohol + amine) is from 100: 0 to 100: 300, and the ratio of the equivalent number of hydroxyalkyl meth (acrylate) to the equivalent number of the free isocyanate group in the reaction product is The range is from 3: 1 to 1: 2.

In the present invention, the reactive resin contains 10 to 80% by weight, especially 30 to 60% by weight of t-butylstyrene. However, this means p-t-butylstyrene, m-t-butylstyrene or a mixture thereof (a ratio of both is preferably about 95: 5).

The t-butyl styrene is also another high boiling comonomer, especially above 120 ° C., preferably 150.
It can also be used as a mixture with (meth) acrylates exhibiting a boiling point above 0 ° C. Quite surprisingly, it has been found that mixtures of unsaturated polyester resins and (meth) acrylate mixtures cure rapidly and completely when they contain t-butylstyrene.

Examples of the methacrylate include 2-ethylhexyl methacrylate, phenylethyl methacrylate, tetrahydrofuryl methacrylate, ethyl triglycol methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminomethyl methacrylate. , 1,4-butanediol dimethacrylate, acetocarboxyalkyl methacrylate, 1,2
-Ethanediol dimethacrylate, isobornyl methacrylate, diethylene glycol, dimethacrylate, methoxypolyethylene glycol monomethacrylate, trimethylcyclohexyl methacrylate, hydroxypropyl methacrylate, dicyclopentyloxyethyl methacrylate are preferred. Butanediol dimethacrylate is particularly preferred.

Acrylate is less preferred because it irritates the skin and lacks stability against hydrolysis.

For example, quartz, glass, corundum, porcelain clay,
Stonewear, barite, gypsum, talc, chalk and the like can be used as reinforcing fillers for reactive resins. sand,
Powders or special shaped bodies (cylindrical, spherical, etc.) are mixed with the synthetic resin solution and / or with a curing agent (initiator). The filler can be used in the form of fibers (fibrous filler). Spherical inert substances are preferred as fillers. This is because the reinforcement hardening is relatively large.

Accelerators, which are preferably arranged spatially with the synthetic resin, ie apart from the curing agent, are generally used for peroxide curing. Suitable accelerators are, for example, N, N-dimethylaniline, N, N-diethylaniline, aromatic amines such as toluidine, N, N-diisopropylideneparatoluidine, N, N-dimethyl-p-.
Toluidine, N, N-bis (2-hydroxyethyl)-
Xylidine, N, N-bis (2-hydroxyethyl)-
Xylidine, such as toluidine, Co, Mn, Sn, C
Examples thereof include salts of e, such as cobalt octoate and naphthenate.

The reactive resin preferably has a viscosity at 23 ° C. of 100 to 10,000, especially 200 to 2000 mPa · s.

In the novel bonding material according to the invention, the curing agent must, of course, be placed separately from the reactive resin. As a preferable curing agent, an organic peroxide having a long shelf life, particularly dibenzoyl peroxide and methyl ethyl ketone peroxide are particularly preferable. Also suitable are t-butyl perbenzoate, cyclohexanone peroxide, lauroyl peroxide, cumyl hydroperoxide and t-butyl peroxide-2-ethylhexanoate.

The peroxide is 0.5 with respect to the reactive resin.
It is preferably used in an amount of from 1 to 10% by weight, especially from 1 to 5% by weight. The hardening agent is preferably an inert filler (preferably quartz sand) which is used after depletion.

In principle, the cartridge preferably has a two-chamber structure. The use of glass cartridges has proven to be preferable. This is because when both components are mixed, they are finely pulverized and always merged and integrated with the reinforcing filler. Ceramic multi-chamber cartridges, such as those described in Nishi Unique Application No. 3929603.2, may also be used.

A reactive resin is contained in the larger chamber of the two-chamber cartridge which is advantageously used, and a curing agent is contained in the smaller chamber together with the filler. In the case of a foamable bonding material, carbonate is added to the active resin, and the other component, acid, is housed in the same chamber together with the curing agent or separately in another chamber.

In addition to the cartridge, of course, it is possible to use, for example, a plastic film as the bonding agent according to the present invention.

The reactive resins containing the novel comonomers polymerized can be used for chemical fixing techniques without being disturbed by malodor and without the need for special care.
The anchors formed by this exhibit good elongation at break, small volume shrinkage, are stable to hydrolysis and heat, and are excellent with mineral foundations such as concrete, rock, foam blocks, and foam bricks. Shows crossed engagement. The viscosity of the reactive resin is low.

Claims (2)

[Claims] 1. A method comprising: (I) a low-release reactive synthetic resin curable by a free radical method and maintained in an isolated state; and (II) a synthetic resin curing agent, wherein the synthetic resin is a comonomer. 10 to 80% by weight of t-
Bonding material for chemically fixing screws in anchor bolts, screwed sleeves or perforations, characterized in that it contains butylstyrene. 2. A cartridge comprising two or more mutually isolated hollow chambers, each of which is loaded with the above synthetic resin and a binder.